CN104449977A - Fuel economy engine oil composition - Google Patents

Abstract

The present invention is directed to a lubricating oil additive containing a vicinal diol and a particular detergent blend typically is low viscosity base oils whereby exhibiting improved fuel economy. In this respect, disclosed is a lubricating oil composition comprising: a major amount of base oil of lubricating viscosity; a friction modifier which is selected from the group consisting of C10-C30 alkane 1,2-diols and C10-C30 alkene 1,2-diols; an overbased alkyl alkaline earth metal hydroxybenzoate detergent having a metal ratio less than 3.0; and an overbased alkyl calcium sulfonate or an overbased alkyl calcium hydroxybenzoate having a metal ratio of 3.5 or greater.

Description

Fuel economy engine oil base oil

Invention field

Disclosed herein is the lubricating oil composition of purification agent mixture having specific vicinal diamines friction improver and have at least two type metal detergents.Described lubricating oil composition demonstrates the rubbing characteristics of improvement and is especially applicable to low-viscosity lubricating oil composition.

Background of invention

Because whole world legislation improves the combination of fuel efficiency and the market requirement, fuel economy has impelled and starts manufacturers to take to change to design (having less tolerance, soakage (boosted intakes) compared with thin tail sheep, fuel direct injection, turbocharger, raising, the engine of start/stop etc.).Additionally, the hardware technology of the mixing of oil electricity and idle running stopping that comprising engine design improvement has proposed the requirement of important new capability to riding automotive engine oil.The not only design effect that must add for these of described automotive engine oil, and engine oil is also regarded as the field that can reach annex performance.Significantly, the fuel economy performance of lubricant is interacted by described oil plant viscosity and additive affected.

In described two factors, viscosity is regarded as causing larger friction minimizing and the factor of fuel economy for a long time.More low viscous machine oil is adopted to be improve the generally acknowledged strategy of vehicle fuel economy.This trend of nearest discovery cannot keep, due to exploitation oil plant viscosity far below consider before those, and therefore can not for continuing.Such as, when using identical chemical composition in formula, go to from the oil plant of SAE viscosity grade 10W-30 the improvement that 5W-30 viscosity oil plant can cause fuel economy to be expected, but go to 0W-20 or lowlyer also do not confirm this trend.The result of a kind of explanation to be this be friction increased when being referred to as boundary lubrication.The situation of these boundary lubrications occurs in when engine runs under low speed and high temperature.Described more low viscous oil plant can not keep the isolation between the moving-member of engine more, and causes increasing friction and reduce fuel economy.In addition, along with lubricant thins out, the misgivings about engine scuffing increase thereupon.

Appropriate addn system is used to become more and more important.Additive in lubricating oil often comprises polar functional group, and described additive " is dragged " metallic surface of engine by it.Due to this interactional reason, known many additives can improve the frictional behaviour of lubricant.Some additives, such as purification agent, known have negative impact by increasing friction to fuel economy.Benefit/potential the shortcoming of the viscosity of the interaction in the lubricant of balance additive and reduction is the challenge to nowadays formulator.

At this, shown that some combination of the friction improver of purification agent and vicinal diamines is found, it demonstrates the fuel economy benefit of increase in conventional oil plant (oil plant of especially low viscous lubricant viscosity).These benefits are proved by stand and testing of engine.

In lubricating oil, adopt vicinal diamines to be well known in the art.US4,406,803 are taught in lubricating oil for IC engines and use C ₁₀-C ₃₀alkane 1,2-glycol is as friction improver.US4,331,222 are taught in functional fluid and use C ₈-C ₂₈alkane 1,2-glycol, in particular for tractor, to reduce brake noise.JP2000-017283 instructs use to be greater than C ₅alkane 1,2-glycol as lubricant.JP2000-273481 instructs C ₁₄-C ₂₂the viscosity index that is combined in that alkane 1,2-glycol and total basicnumber are greater than the purification agent of 60 is be used for lubrication in the base oil of 80-150.WO2010/115864 is taught in functional fluid and uses C ₁₀-C ₂₄glycol, is particularly useful for wet brake.WO20111007643 is taught in the combination of alkane or chain base 1,2-glycol and zinc dithiophosphate in lubricant to improve fuel economy.The friction improver class comprising alkane/alkene 1,2-glycol employs decades.But, none problem for the improvement that rubs in very low viscous machine oil of before described lubricant.

Summary of the invention

One aspect of the present invention relates to the lubricating oil additive containing vicinal diamines and specific purification agent blend typically in low viscous base oil, shows the fuel economy of improvement thus.At this on the one hand, lubricating oil composition disclosed herein comprises: the lubricant viscosity base oil of primary amount; Be selected from C ₁₀-C ₃₀alkane 1,2-glycol and C ₁₀-C ₃₀the friction improver of alkene 1,2-glycol; Metal ratio lower than 3.0 parlkaline alkyl hydroxy phenylformic acid alkaline earth salt purification agent; Metal ratio is parlkaline alkylsulphonic acid calcium or the parlkaline alkyl hydroxy calcium benzoate of 3.5 or higher.In further one, described alkaline-earth metal is calcium.

Relate in one aspect to lubricating oil composition, wherein said vicinal diamines friction improver is selected from formula R ₁-CH (OH) CH ₂(OH), wherein R ₁for the alkyl containing 10-28 carbon atom.The C of to be wherein said friction improver disclosed in the present invention be more specifically the linear alkyl derived from containing 14-18 carbon atom ₁₀-C ₃₀alkane 1,2-glycol.About this point, the amount that described friction improver is typically about 5.0wt.% with about 0.02-uses, based on the gross weight of described lubricating oil composition.

Relate in one aspect to lubricating oil composition, it comprises: the lubricant viscosity base oil of primary amount; Be selected from C ₁₀-C ₃₀alkane 1,2-glycol and C ₁₀-C ₃₀the friction improver of alkene 1,2-glycol; Metal ratio lower than 3.0 parlkaline alkyl hydroxy phenylformic acid alkaline earth salt purification agent, its alkyl chain length is 14-18 carbon atom; With parlkaline alkylsulphonic acid calcium or parlkaline alkyl hydroxy calcium benzoate that metal ratio is 3.5 or higher.In further one, described alkyl chain is linear alkyl.In further one, described alkaline-earth metal is selected from calcium.

Relate in one aspect to lubricating oil composition, it comprises: the lubricant viscosity base oil of primary amount; Be selected from C ₁₀-C ₃₀alkane 1,2-glycol and C ₁₀-C ₃₀the friction improver of alkene 1,2-glycol; Metal ratio lower than 3.0 parlkaline alkyl hydroxy phenylformic acid alkaline earth salt purification agent; With parlkaline alkylsulphonic acid calcium or parlkaline alkyl hydroxy calcium benzoate that metal ratio is 3.5 or higher, its alkyl chain length is 20-28 carbon atom.One further in, described metal ratio be 3.5 or higher purification agent be parlkaline alkyl hydroxy calcium benzoate; On the other hand, described metal ratio is the purification agent of 3.5 or higher is parlkaline alkylsulphonic acid calcium.

One aspect of the present invention relates to the feature of described base oil, and therefore, on the one hand, the viscosity index of described lubricant viscosity base oil is greater than 110.More specifically, selection described lubricant base 150 DEG C according to ASTM D4683 measure HTHS viscosity lower than 2.9mPas.Other the feature this kind of of described base oil and additive can be chosen such that to make to prepare described lubricating oil composition to meet SAE viscosity grade 0W20.Lower viscosity in the selection of suitable base oil for lubricating oil composition of the present invention provides the improvement of rubbing characteristics, therefore relate in one aspect to wherein said lubricating oil composition can have according to ASTM D4683 measure HTHS viscosity 150 DEG C lower than the lubricant base of 2.6mPas and even wherein said lubricant base have according to ASTM D4683 mensuration HTHS viscosity at 150 DEG C lower than 2.3mPas.In this respect, described lubricating oil composition can be prepared to contain the viscosity index improver component lower than 3wt%.In further one, described lubricating composition is substantially devoid of viscosity index improver component.

An aspect of of the present present invention relates to the lubricating oil composition of fuel economy, and it is particularly useful for lubricating internal combustion engines, such as, be installed on diesel motor, the petrol engine of land travelling vehicle, and gas engine.About this point, disclosed herein is lubricant composition for internal combustion engine, and it comprises: the lubricant viscosity base oil of primary amount; Amount is the C of about 0.1-3 quality % ₁₀-C ₃₀alkyl 1,2-glycol; In alkaline-earth metal, measure into about 0.01-0.4 quality % metal ratio lower than 3.0 parlkaline alkyl (C ₁₄-C ₁₈) hydroxy-benzoic acid alkaline earth salt purification agent; In calcium, the metal ratio measured as 0.01-0.4 quality % is the parlkaline alkyl (C of 3.5 or higher ₂₀-C ₂₈) calcium sulphonate or parlkaline alkyl (C ₂₀-C ₂₈) calcium hydroxybenzoate; By nitrogen content, measure the nitrogenous dispersion agent into about 0.01-0.3 quality %; By phosphorus content, measure the zinc dialkyl dithiophosphate into 0.01-0.1%; Amount is the oxidation retarder being selected from phenolic antioxidant or diphenylamine oxidation inhibitor (or their mixture) of 0.1-7 quality %; With the total amount that wherein said quality % is based on described lubricating oil composition.

Describe in detail

Described term " basic metal " refers to lithium, sodium or potassium.

Described term " alkaline-earth metal " refers to calcium, barium, magnesium and strontium.

Described term " alkyl aryl sulphonic acid alkaline earth salt " refers to the alkaline earth salt of alkyl aryl sulphonic acid.In other words, the alkaline earth salt of this aryl replaced by the sulfonic acid group that (1) alkyl group and (2) can form metal-salt.

Described term " alkyl " refers to the alkyl group of straight chain and side chain.

Described term " alkyl phenate " refers to the metal-salt of alkylphenol.

Described term " alkylphenol " refers to the phenol with one or more alkyl substituent, the carbon atom one of at least in wherein said alkyl substituent with enough numbers with to carbolic oil dissolubility.

Described term " aryl " replaces or unsubstituted aryl, such as phenyl, tolyl, xylyl, ethylphenyl and cumyl.

Described term " calcium alkali " refers to calcium hydroxide, calcium oxide, alcohol calcium etc., and their mixture.

Described term " alkyl " refers to containing carbon and hydrogen atom and by carbon atom bonding to the group of molecule remainder or free radical.It can contain heteroatoms, and namely except the atom of carbon and hydrogen, condition is that they do not change the essential property of hydrocarbon and the characteristic of described group.As the example of alkyl, the alkyl that can mention and alkenyl.

Described term " alkyl phenol " refers to the phenol with one or more hydrocarbyl substituent; The carbon atom one of at least in described hydrocarbyl substituent with enough numbers with to carbolic oil dissolubility.

Described term " lime " refers to calcium hydroxide, is also called white lime (slaked lime) or slaked lime (hydrated lime).

Described term " metal " refers to basic metal, alkaline-earth metal or their mixture.

Described term " metal base " refers to metal hydroxides, metal oxide, metal alkoxide etc. and their mixture, and wherein said metal is selected from lithium, sodium, potassium, magnesium, calcium, strontium, barium or their mixture.

Described term " parlkaline " refers to metalloid salt or a complex compound.These materials are also called " alkalescence ", " hyperalkaline (superbased) ", " high alkalinity (hyperbased) ", " complex compound ", " metal complex ", " high metal content salt " etc.Parlkaline product is metal-salt or complex compound, it is characterized in that metal content has exceeded according to metal and the metal content that should exist with the stoichiometry of the specific acidic organic compound (such as carboxylic acid) of this metal reaction.

Described term " phenates " refers to the metal-salt of phenol.

With the milligramequivalent number of the KOH of 1 gram of sample needs during described term " total basicnumber " or " TBN " refer to.Therefore, high TBN reflects strong peralkaline product, and thus more polybase is laid in neutralizing acid.The TBN of product can measure by ASTM D2896 or equivalent method.

Described term " SAE J300 " refers to the SAEJ300 of the version in January, 2009: " EngineOil Viscosity Classification ".

Hydrocarbon based diol:

Expect that the described hydrocarbon based diol used in the present invention is the hydrocarbon based diol with vicinal hydroxyl groups.They have following formula: R-(OH) ₂wherein R is the hydrocarbyl group containing 10-30 carbon atom, comprises their mixture.R can be linear or branching, saturated or undersaturated.Especially, R is straight chained alkyl or kiki alkenyl group, and wherein said kiki alkenyl group has two or less unsaturated link(age), single unsaturated link(age).Described two oh groups preferably close to hydrocarbyl chain end and on adjacent carbon atom (ortho position).

As disclosed above, described preferred vicinal diamines contains 10-30 carbon atom.This scope is preferred, has significantly lower antifriction character owing to having far below the glycol of 10 or 12 carbon atoms, simultaneously have more than 30 carbon atoms those in, deliquescent constraint becomes remarkable.More preferably C ₁₄-C ₁₈the mixture of hydrocarbyl group and this hydrocarbyl group, solvability, rubbing characteristics and other character seem to be maximized wherein.

Preferred vicinal diamines formula R ₁-CH (OH) CH ₂(OH) alkane-1,2-glycol representative, wherein R ₁the alkyl containing 8-28 carbon atom or their mixture.Straight chain and branched alkyl group can be adopted.What be particularly useful is the mixture of linear alpha-olefin or linear alpha-olefin, is terminal olefine, contrasts with internal olefin.Described preferred linear alpha-olefin is the alpha-olefin cut of the n-alpha-olefin with primary amount.As used herein, primary amount refers to the n-alpha-olefin being greater than about 50wt%, and is preferably more than about 80wt%.The example of described alpha-olefin comprises 1-decene, 1-undecylene, 1-dodecylene, 1-tridecylene, tetradecene, 1-15 carbene, cetene, 1-heptadecene, 1-vaccenic acid, 1-19 carbene, 1-eicosylene, 1-heneicosene, 1-bis-dodecylene, 1-tetracosene etc.Spendable commercially available alpha-olefin cut comprises C _15-18alpha-olefin, C _12-16alpha-olefin, C _14-16alpha-olefin, C _14-18alpha-olefin, C _16-18alpha-olefin, C _16-20alpha-olefin, C _18-24alpha-olefin, C _20-24alpha-olefin, C _22-28alpha-olefin, C _24-28alpha-olefin, C _26-28alpha-olefin etc.Suitable n-alpha-olefin can derive from ethylene chain and increase technique.The straight chain 1-alkene of this technique output even number from the reaction of controlled Ziegler polymerization.The oligomeric route that non-Ziegler ethylene chain increases also is well known in the art.Other method preparing alpha-olefin of the present invention comprises the catalytic dehydrogenation of wax cracking and normal paraffin.But, after these techniques usually require that further processing technology is to provide suitable alpha-olefin carbon distribution.

Can adopt the glycol of single carbon number, such as decane-1,2-glycol, octadecane-1,2-glycol, eicosane-1,2-glycol, triacontane-1,2-glycol etc., but the mixture of several carbon numbers is preferred.Typical mixture comprises 1,2-glycol of the individual carbon atom chain alkyl of 10-30 (comprising cut off value); 12,1,2-glycol of 14,16,18 and 20 carbon atom alkanes; 1,2-glycol of the individual carbon atom alkane of 15-20 (comprising cut off value); 1,2-glycol of the individual carbon atom alkane of 15-18 (comprising cut off value); 1,2-glycol of the individual carbon atom alkane of 20-24 (comprising cut off value); 24,1,2-glycol of 26 and 28 carbon atom alkanes; 1, the 2-glycol etc. of the individual carbon atom alkane of 16-18 (comprising cut off value).

The useful glycol of the present invention is commercially available or easily prepares from corresponding 1-alkene by means commonly known in the art.Such as, described alkene first with peracid as Peracetic Acid or hydrogen peroxide add that formic acid reacts to form alkane-1,2-epoxide, alkyl group-1,2-epoxide acid or base catalysis under be easily hydrolyzed to alkane-1,2-glycol.In other method, described alkene first halogenation is the two halo-alkane of 1,2-and is hydrolyzed to alkane-1,2-glycol by first reacting with sodium-acetate and then reacting with sodium hydroxide subsequently.Vicinal diamines can also be prepared by peroxy trifluoroacetic acid method, and the hydroxylation of other program is known and can be found in U.S. Patent No. 2,411,762; 2,457,329 and 2,455,892.Described glycol can also be prepared by being hydrolyzed subsequently by the catalysis epoxidation of suitable alkene.

The particularly preferred glycol expected is 1,2-decane glycol, 1,2-dodecanediol, 1,2-tetradecane diols, 1,2-pentadecane diols, 1,2-hexadecane diol, 1,2-heptadecane diols, 1,2-octadecandiol etc., 1,2-C of mixing ₁₅-C ₁₈alkanediol, mixing 1,2-C ₁₃-C ₁₆alkanediol, mixing 1,2-C ₁₆-C ₁₈alkanediol, and the mixture of all this kind of glycol, comprise the mixture of similar glycol.Other suitable glycol is derived from C12-16 alpha-olefin, C14-16 alpha-olefin, C14-18 alpha-olefin, and C16-20 alpha-olefin business cut.

Purification agent mixture:

Described purification agent mixture at least comprises metal ratio and is less than or equals the first overbased metal alkyl-substituted hydroxy-benzoic acid salt of 3.Purification agent mixture also comprise the metal ratio different from described first purification agent be more than or equal to 3.5 the second metal detergent.Described second purification agent is overbased metal alkyl-substituted hydroxy-benzoic acid salt or overbased metal alkylaryl sulphonate.

Described overbased metal alkyl-substituted hydroxy-benzoic acid salt typically has following structure:

Wherein R _afor linear aliphatic race group, the aliphatic group of branching or aliphatic group mixture that is linear and branching.More than one R can be had _agroup is connected to phenyl ring, however dialkyl group connect lower than 5% and expection do not change performance.Preferably, R _aalkyl or kiki alkenyl group.More preferably, R _ait is the alkyl group of the straight or branched with 9-40 carbon atom.Work as R _awhen being linear aliphatic race group, described linear alkyl group typically comprises an about 12-40 carbon atom, more preferably from about 14-30 carbon atom.Work as R _awhen being the aliphatic group of branching, the alkyl group of described branching typically comprises at least 9 carbon atoms, preferably an about 9-24 carbon atom and most preferably from about 10-18 carbon atom.The aliphatic group of this branching preferably derives from the oligopolymer of propylene or butylene.

R _aalso can represent the mixture of the aliphatic group of linear or branching.Work as R _awhen representing the mixture of aliphatic group, alkaline-earth metal alkyl hydroxy phenylformic acid of the present invention can containing the mixture of linear group, the mixture of branched groups, or the mixture of the group of linear and branching.Therefore, R _acan be the mixture of linear aliphatic race group, preferred alkyl; Such as, C is selected from ₁₄-C ₁₆, C ₁₄-C ₁₈, C ₁₆-C ₁₈, C ₁₈-C ₂₀, C ₂₀-C ₂₂, C ₂₀-C ₂₄and C ₂₀-C ₂₈the alkyl of alkyl and their mixture, and derived from positive alhpa olefin.Advantageously, these mixtures comprise at least 95 % by mole, preferably the alkyl group being derived from vinyl polymerization of 98 % by mole.

M is the alkaline-earth metal being selected from calcium, barium, magnesium, strontium.Calcium and magnesium are preferred alkaline-earth metal.Calcium is preferred.Wherein y and z is integer or mark independently.

In formula-and COOM group can be positioned at the ortho position of described oh group, a position or contraposition, and wherein said ortho position is preferred on the one hand.Described R _agroup can be positioned at the ortho position of described oh group, a position or contraposition.

Alkyl hydroxy phenylformic acid alkaline earth salt of the present invention can be at ortho position, a position or contraposition have the benzoic any mixture of alkaline-earth metal alkyl hydroxy of COOM group.

Alkyl hydroxy phenylformic acid alkaline earth salt of the present invention is solvable usually in oil, it can be characterized by following test: 600 neutral diluent oil and be the mixture of the alkyl hydroxy benzoate of 10wt% at 60 DEG C of temperature centrifugal 30 minutes based on the total weight content of described mixture, this centrifugal carrying out under standard A STM D2273 defined terms (should be noted that centrifugal is do not having to carry out under the condition of diluting, that is, solubilizing agent is not had); Measure the sedimental volume formed after centrifugation at once; If this settling is less than 0.05%v/v (the sedimental volume relative to described volume of mixture), this product is just considered to solvable in oil.

Hydroxy-benzoic acid typically by phenates by Carboxylation effect, prepared by Kolbe-Schmitt technique, and in this case, usually obtain with the form of the mixture with not Carboxylation phenol (usually in thinner).Hydroxy-benzoic acid can be unvulcanized or sulfuration, and can be chemically modified and/or contain other substituting group.The technique of sulfuration alkyl-substituted hydroxy-benzoic acid be those skilled in the art known, and to be described in such as U.S. Patent application No.2007/0027057.

Described term " parlkaline " is usually used to describe metal detergent, and metal ratio (ratio of metallic member equivalents and acid moieties equivalents) is greater than 1 wherein.Described term ' low alkalinity ' is used to describe metal detergent, and this metal ratio is greater than 1 wherein, and at the most about 2.5.

" the parlkaline calcium salt of tensio-active agent " refers to overbased detergent, and the metallic cation of the insoluble metal-salt of described oil is calcium positively charged ion substantially wherein.Other positively charged ion a small amount of may reside in oily insoluble metal-salt, but in the insoluble metal-salt of oil typically at least 80, more typically at least 90, the positively charged ion of such as at least 95 % by mole is calcium ion.Positively charged ion except calcium can derive from and use in the overbased detergent manufacture of such as surfactant salt, and this positively charged ion is the metal except calcium wherein.Preferably, the metal-salt of this tensio-active agent is also calcium salt.

The overbased metal purification agent of carbonating typically comprises amorphous nano particle.In addition, the nano-particle material comprising the carbonate of corn spar and vaterite form also has open.

The basicity of purification agent can also be expressed as total basicnumber (TBN).Total basicnumber is measuring of described parlkaline material alkalescence.It is described to the milligram number of the KOH of every gram of material.TBN can use ASTM standard D2896 or equivalent method to measure.Described purification agent can have low TBN (that is, TBN is lower than 100), medium TBN (that is, TBN is 100-250) or high TBN (that is, TBN is greater than 250, such as 250-500).

Any technology preparation that overbased metal alkyl-substituted hydroxy-benzoic acid salt adopts by this area.Usual method is as follows: 1. in the solvent mixture comprising volatile hydrocarbon, alcohol and water, produces slight overbased metal alkyl-substituted hydroxy-benzoic acid salt complex with in the metal base of molar excess with alkyl-substituted hydroxy-benzoic acid; 2. carbonating is with the metal carbonate of production colloidal state-dispersion, is rear duration of response subsequently; 3. remove non-colloidal dispersion remaining solid; With 4. strippings to remove the solvent in process.

Overbased metal alkyl-substituted hydroxy-benzoic acid salt is by interval or overbased technology preparation continuously.

Metal base (such as, metal hydroxides, metal oxide or metal alkoxide), preferred lime (calcium hydroxide), can add in one or more stage.The reinforced of metal base can be identical or different, and the carbonic acid gas added subsequently also can be like this.When adding calcium hydroxide further and feeding in raw material, the carbon dioxide treatment of last stage need not to be completely.Along with the carrying out of carbonating, the oxyhydroxide of dissolving is converted into the colloidal state carbonate particle in the mixture being scattered in non-volatile hydrocarbon solvent and non-volatility hydrocarbon ils.

Carbonating can be carried out in one or more stage in the temperature range of the reflux temperature of alcohol promotor at the most.Intensification can be similar, or different, or can change in each temperature rise period.The stage that temperature raises and optionally then reduces, can before further carbonation step.

The non-volatile hydrocarbon solvent of described reaction mixture is preferably the liquid aromatic hydrocarbons that boiling point is not more than the routine of about 150 DEG C.Found that aromatic hydrocarbons provides some benefit, the filtering rate such as improved, and the example of suitable solvent is toluene, dimethylbenzene and ethylbenzene.

Described alkanol is preferably methyl alcohol, although other alcohol such as ethanol also can use.The selecting properly of alkanol-hydrocarbon solvent ratio and the water-content of initial action mixture are important for obtaining the product expected.

Oil can join in reaction mixture; If like this, suitable oil comprises hydrocarbon ils, those of especially mineral origin.At 38 DEG C, there is 15-30mm ²the oil of the viscosity of/s is most suitable.

After finally processing with carbonic acid gas, usually reaction mixture is heated to high temperature, such as, is greater than 130 DEG C, to remove volatile materials (water and any residual alkanol and hydrocarbon solvent).When synthesis completes, owing to there is suspended sediment, crude product is muddy.By such as filtering or centrifugally making it clarify.These measures can before solvent removing, or on middle opportunity, or use afterwards.

Product uses usually used as oil solution.If reaction mixture contains inadequate oil to keep oil solution after removing volatile matter, then should add oil again.This can before solvent removing, or on middle opportunity, or carry out afterwards.

Advantageously, the TBN of medium parlkaline alkyl hydroxy phenylformic acid alkaline earth salt of the present invention is about 100-250, is preferably about 140-230 and usually has lower than 1 volume %, preferably lower than the rough deposit of 0.5 volume %.About this point, medium parlkaline alkyl hydroxy phenylformic acid alkaline earth salt of the present invention can be single purification agent or mixture.On the one hand, use metal ratio lower than 3.0, preferably lower than 2.5 lower TBN (about 140-175); About this point, preferred alkyl chain is derived from the linear alpha-alkene with 14-18 carbon atom.On the other hand, can adopt TBN be about (200-240), metal ratio be greater than 4.0 the second medium parlkaline alkyl hydroxy phenylformic acid alkaline earth salt (together with the material of lower TBN or substitute the material of lower TBN); About this point, preferred alkyl chain is derived from the linear alpha-alkene with 20-28 carbon atom.The TBN exceeding alkaline alkyl hydroxy-benzoic acid alkaline earth salt of the present invention is greater than 250, be preferably about 250-450 and more preferably from about 300-400 and usually have lower than 3 volume %, preferably lower than 2 volume % with more preferably lower than the rough deposit of 1 volume %.The metal ratio of the material of this higher TBN is greater than 6, and preferably about 8; About this point, preferred alkyl chain is derived from the linear alpha-alkene with 20-28 carbon atom.

Except this paper one or more overbased metal alkyl-substituted hydroxy-benzoic acid salt above-described, suitable purification agent in addition can be selected from typical detergent for lubricating oil; With as used herein, it is different from described first purification agent.The common example of metal detergent comprises: sulfonate, alkyl phenate, alkyl monosulfide phenates, carboxylate salt, salicylate, phosphonate and phosphinates.Overbased metal sulphonate is produced by the carbonating of the mixture by hydrocarbon, sulfonic acid, metal oxide or oxyhydroxide (such as calcium oxide or calcium hydroxide) and promotor (such as dimethylbenzene, first alcohol and water) usually.Such as in order to prepare overbased calcium sulfonate, in carbonating, the carbon dioxide reaction of calcium oxide or calcium hydroxide and gaseous state is to form calcium carbonate.With in excessive CaO or Ca (OH) and sulfonic acid to form sulfonate.Currently known methods for the prior art crossing alkaline calcium sulfonate produces high alkaline reserve usually, and TBN is 300-400mgKOH/gm or higher.Commercially available high TBN, approximately the sulfonate of 400TBN makes formulator that the sour neutralization additive of relatively low amount can be used to keep the spatter property of equivalence simultaneously at the most, and therefore adequately protect engine in combustion under the condition of peracidity thing formation.Disclose on the one hand the improvement parlkaline alkyl hydroxy phenylformic acid alkaline earth salt of high TBN sulfonate (be greater than 400TBN, metal ratio is 16 or higher) and lower metal ratio being applied to vehicle crankcase machine oil formula and can causing fuel economy.

Also being included in " sulfonate " implication is the sulfonate of alkylaryl compounds of synthesis, and it is often preferred.These acid are also by preparing with sulfuric acid or sulphur trioxide process alkylaryl compounds.As mentioned above, at least one alkyl substituent of aromatic ring is oil-soluble group.The acid of acquisition like this is called as the alkyl aryl sulphonic acid of synthesis and described salt is called as alkylaryl sulphonate.Wherein alkyl is the sulfonate of straight chain is known linear alkyl arylsulphonate.Typically these become C by ethylene oligomerization ₁₄-C ₄₀hydrocarbon, reacts alkylation by Friedel and Craft of aromatic hydrocarbons subsequently and obtains.The alkene of branching can become C from such as oligomeric acrylamide ₁₅-C ₄₂hydrocarbon and particularly propylene tetramer two are polymerized to C ₂₄alkene, or use the alkylation of the aromatics of positive alpha-olefin to obtain.Preferred aromatic yl group is phenyl and substituted-phenyl, preferred tolyl, xylyl, especially o-Xylol base, ethylphenyl, cumyl etc.

The basic metal of the acid-utilising alkali reaction obtained by sulfurization or alkaline earth metal compound neutralization change into metal-salt with output I race or II race metal sulfonate.Usually, acid-utilising alkali metal base neutralization.Alkaline earth salt is obtained from an alkali metal salt by replacement(metathesis)reaction.Alternately, sulfonic acid utility alkali earth metals alkali directly neutralizes.Sulfonate is then alkalized by crossing and the method for this parlkaline material and this material of preparation is known to those skilled in the art.See the LeSuer U.S. Patent No. 3,496,105 such as issued on February 17th, 1970, especially the 3rd and 4 hurdles.

Described sulfonate is present in described lubricating oil composition with the form of alkaline earth salt or their mixture.Described alkaline-earth metal comprises magnesium, calcium and barium, and wherein calcium is preferred.Described sulfonate adopts excessive alkali metal base, carbonic acid gas or other suitable alkali source to surpass alkalization.This is usually add in order or progressively add, be with or without promotor, gives alkalinization and pays close attention to especially, and this is because inappropriate alkalinization of crossing is by the full-bodied sulfonate caused or than expecting low parlkaline.

But, due to their availability widely, especially preferred is the salt of mahogany acid, particularly by the salt of mahogany acid that the various hydrocarbon-fraction of sulfonation such as lubricating oil distillate and the extract that is rich in aromatics obtain, the described extract being rich in aromatics obtains by extracting hydrocarbon ils with selective solvent, and they and alkene or alkyl chloride can to react by alkylation catalyst and carry out alkylation by described extract (if desired) before sulfonation; Can or can not the salt etc. of alkylating organic many sulfonic acid such as benzene disulfonic acid.

The preferred salt that the present invention uses is the salt of alkylated aromatic sulfonic acid, and wherein said one or more alkyl contains at least about 8 carbon atoms (such as an about 8-40 carbon atom).Another of sulfonate parent material is preferably organized as aliphatics-substituted cyclic sulfonic acid, wherein aliphatic substituting group or substituting group are altogether containing at least 12 carbon atoms, such as alkyl aryl sulphonic acid, alkyl cyclic aliphatic sulfonic acid, alkyl heterocycle sulfonic acid and aliphatic sulfonic, wherein one or more aliphatic groups are altogether containing at least 12 carbon atoms.The concrete example of these oil-soluble sulfonic acid comprises mahogany acid, vaseline sulfonic acid, single-and many-wax-replacement naphthene sulfonic acid, substituted sulfonic acid is cetyl benzenesulfonic acid, hexadecyl phenylbenzimidazole sulfonic acid etc. such as, aliphatic sulfonic is paraffin sulfonic acid, hydroxyl-replacement paraffin sulfonic acid etc. such as, cyclic aliphatic sulfonic acid, petronaphthalene sulfonic acid, hexadecyl cyclopentyl sulfonic acid, single-and many-wax-substituted cyclohexyl sulfonic acid etc.Described term " mahogany acid " intention contains all natural sulfonic acid directly deriving from petroleum product.The II race metal sulfonate being typically suitable for said composition comprises the following metal sulfonate of example: white oil Phenylsulfonic acid calcium, white oil barium benzosulfonate, white oil Phenylsulfonic acid magnesium, propylene dimer Phenylsulfonic acid calcium, propylene dimer barium benzosulfonate, propylene dimer Phenylsulfonic acid magnesium, calcium mahogany sulfonate, barium mahogany sulfonate, petrolic magnesium sulfonate, triacontyl calcium sulphonate, triacontyl sulfonate magnesium, dodecyl sodium sulfonate calcium, dodecyl sodium sulfonate barium, dodecyl sodium sulfonate magnesium etc.

The alkylaryl sulphonate further preferably synthesized.What be particularly useful is have the aryl sulfonic acid root of 1 or 2 that is connected to alkyl group, be preferably greater than 5 % by mole, be more preferably greater than 13 % by mole and be more preferably greater than the synthesis of alkyl arylsulphonate of 20 % by mole, because these have shown good consistency and solvability, do not formed skin in the parlkaline of these levels simultaneously.Preferably linear monoalkyl sulfonate.Preferred alkyl chain contain 14-40 carbon and more preferably this alkylaryl sulphonate derive from C ₁₄-C ₄₀positive alpha-olefin and more specifically derive from C ₂₀-C ₂₈or C ₂₀-C ₂₄positive alpha-olefin.About this point, alkylaryl sulphonate derives from C ₂₀-C ₂₈or C ₂₀-C ₂₄positive alpha-olefin and by parlkaline such as, to have high TBN (namely TBN is greater than 250,250-500), preferable alloy ratio is more than or equal to 8, preferably 10-20, more preferably 16-18.

The mixture of high TBN sulfonate can be adopted, comprise the mixture of the sulfonate of natural sulfonate and synthesis, the mixture of mixture such as monoalkyl and dialkyl group sulfonate of the sulfonate of synthesis, the mixture of monoalkyl and many alkylsulfonates or dialkyl group and many alkylsulphonic acids salt mixture.

Lubricating oil composition

The invention still further relates to the lubricating oil composition containing hydrocarbon based diol of the present invention and parlkaline alkylate hydroxyl aromatic carboxylic acid salt purification agent mixture.This kind of lubricating oil composition is by the hydrocarbon based diol of the present invention of the lubricant viscosity base oil and minor amount that comprise primary amount and parlkaline alkylate hydroxyl aromatic carboxylic acid salt purification agent mixture.

Base oil used herein is defined as the blend of basestocks or basestocks, and described basestocks is the lubricant composition being produced extremely same specification (not relying on to material source or manufacturer place) by single manufacturers; It meets the specification of identical manufacturers; And its can by the formula of uniqueness, product ID or both identify.Basestocks can use much different technique to produce, and described technique includes but not limited to distillation, solvent treatment, hydrogen process, oligomeric, esterification, and re-refines.The oil plant re-refined should be substantially free of the material introduced by manufacture, pollution or use before.Base oil of the present invention can be the lubricating base oil fractions of natural or synthesis arbitrarily, and especially kinematic viscosity is those of about 4 centistoke (cSt)-Yue 20cSt at 100 DEG C.Hydrocarbon synthetic oil can comprise such as by ethene, poly-alpha olefins or PAO polymerization or by the oil using the hydrocarbon building-up process (such as in Fischer-Tropsch method) of carbon monoxide and hydrogen to prepare.Preferred base oil comprises a small amount of (if any) mink cell focus, and such as a small amount of (if any) viscosity is the base oil of the lubricating oil distillate of about 20cSt or higher at about 100 DEG C.Can select according to the end-use expected and additive in processed oil or the blended oil plant being used as described base oil with the grade providing machine oil to expect, such as, the SAE viscosity grade of lubricating oil composition is 0W-20,0W-30,0W-40,0W-50,0W-60,5W, 5W-20,5W-30,5W-40,5W-50,5W-60,10W, 10W-20,10W-30,10W-40,10W-50,15W, 15W-20,15W-30, or 15W-40.

On the one hand, the present invention relates to and use comparatively low viscosity grade.Engine hardware and in manufacturing nearest improvement allow in vehicle, use comparatively low viscosity grade to keep weather resistance simultaneously, and provide new for the fuel economy sexual demand increased.These refer to the low viscous passenger car engine oil base oil of super-in this article.

Base oil can derive from Natural lubricating oils, ucon oil or their mixture.Suitable base oil comprises the basestocks obtained by synthetic wax and slack wax (slack wax) isomerization, and the isocrackate basestocks by making the aromatics of crude oil and polar compound hydrocracking (instead of solvent extraction) produce.Suitable base oil comprises as API publication the 1509,14th edition, Addendum I, those base oils in all API classifications defined in December, 1998 and I, II, III, IV and V.IV class base oil is poly-alpha olefins (PAO).V class base oil comprises all base oils not included in other in I, II, III or IV class.III class base oil is preferred, and the mixture of II/III class and the mixture of III/IV class are also preferred.

The common mixture of base oil can be adopted.II class basestocks contains the stable hydrocarbon being more than or equal to 90%; Be less than or equal to the sulphur of 0.03%; 80 are more than or equal to and lower than 210 with viscosity index.The manufactory manufacturing II class basestocks typically adopts hydrotreatment such as hydrocracking or violent hydrotreatment with the value of the VI to regulation that increase crude oil.The content of stable hydrocarbon is typically increased to more than 90% and reduce to sulphur lower than 300ppm by the use of hydrotreatment.The II class basestocks kinematic viscosity used in the present invention is about 2-14cSt at 100 DEG C.

III class basestocks contains the stable hydrocarbon being more than or equal to 90%; Be less than or equal to the sulphur of 0.03%; With the viscosity index being more than or equal to 120.Usual use three stage process produces III class basestocks, and described three stage process comprise hydrocrackates raw material such as vacuum gas oil makes all aromatics that may exist saturated with the lube stock of the height paraffinic hydrocarbons producing very high viscosity index (HVI) with removal of impurity; Make the oil plant of hydrocracking stand selective catalytic hydrogenation dewaxing, n-paraffin is converted into branched paraffin by isomerization by it; Hydrofining is subsequently to remove any residual aromatics, sulphur, nitrogen or oxygenatedchemicals.The present invention's spendable III class basestocks is about 3-9cSt the kinematic viscosity of 100 DEG C.

IV class low viscosity base oil can be incorporated in formula.

Relate in one aspect to the low viscosity passenger car engine oil base oil that kinematic viscosity is 3-9.3cSt at 100 DEG C, more preferably wherein said composition kinematic viscosity is 3-8.2cSt at 100 DEG C, the Noack volatility measured by ASTMD5800 is lower than 15%, the CCS viscosity measured by ASTM D5293 at-35 DEG C lower than 5120cP, with the HTHS viscosity measured by ASTM D4683 at 150 DEG C lower than 2.9mPas, the HTHS viscosity more preferably measured by ASTM D4683 at 150 DEG C less than or equal to 2.6mPas.Relate in one aspect to low viscosity passenger vehicle engine, the kinematic viscosity of wherein said engine oil base oil is 4-6.9cSt at 100 DEG C, the Noack volatility measured by ASTM D5800 is lower than 15%, the CCS viscosity measured by ASTM D5293 at-35 DEG C lower than 4820cP, and the HTHS viscosity measured by ASTM D4683 at 150 DEG C lower than 2.6mPas.

Natural lubricating oils can comprise animal oil, vegetables oil (such as, rapeseed oil, Viscotrol C and lard), petroleum oil, mineral oil, and the oil plant deriving from coal or shale.The oil plant of synthesis can comprise that hydrocarbon ils and halogen-replacement hydrocarbon ils be such as polymerized with alkene that is copolymerization, alkylbenzene, polyphenyl, alkylated dipheny ethers, alkylated diphenyl sulfides and their derivative, analogue and homologue etc.Ucon oil also comprises alkylene oxide polymer, interpretation, multipolymer and their derivative, and wherein terminal hydroxy groups is by the modification such as esterification, etherificate.Another kind of suitable ucon oil comprises the ester of dicarboxylic acid and various alcohol.The ester that can be used as synthesizing oil plant also comprises by C ₅-C ₁₂ester prepared by monocarboxylic acid and polyvalent alcohol and polyol ethers.Those illustrated in trialkyl phosphate ester oil such as TRI N BUTYL PHOSPHATE and three iso-butyl ester of phosphoric acid are also suitable as base oil.

Silicon-based oil (such as poly-alkyl-, poly-aryl-, poly-alkoxyl group-or poly-aryloxy silicone oil and silicic acid ester oil) form another kind of useful ucon oil.Other ucon oil comprises the liquid ester of phosphorous acid, the tetrahydrofuran (THF), poly-alpha olefins etc. of polymerization.

Described base oil can derive from not refining, refining, rerefined oils, or their mixture.Unrefined oil directly derives from natural source or synthetic source (such as, coal, shale, or tar sand bitumen), without the need to being further purified or processing.The example of unrefined oil comprises the shale oil directly deriving from retorting operation, the petroleum oil directly deriving from distillation or directly derives from the ester oil of esterification process, its each can directly use (without the need to further process).Treated oil and unrefined oil similar, except treated oil processes to improve one or more character in one or more purification steps.Suitable purification technique comprises distillation, hydrocracking, hydrotreatment, dewaxing, solvent extraction, acid or alkaline extraction, filtration and diafiltration, and these technology are known in those skilled in the art.Rerefined oils is by being undertaken processing obtaining by those methods be similar to for obtaining treated oil by used oil.These rerefined oils are also called recovered oil or reprocessed oils and process in addition frequently by the technology for removing useless additive and oil decomposition (breakdown) product.

Base oil derived from wax hydroisomerization also can be used alone or combinationally uses with above-mentioned base oil that is natural and/or that synthesize.This wax isomer oil is by the hydroisomerization production in hydroisomerisation catalysts by the wax of natural or synthesis or their mixture.

The base oil of primary amount is preferably used in lubricating oil composition of the present invention.The base oil of primary amount defined herein comprises 50wt% or more.The preferred amounts of base oil accounts for the about 50wt%-97wt% of lubricating oil composition, more preferably from about 60wt%-97wt% and most preferably from about 80wt%-95wt%.(as operating weight % herein, except as otherwise noted, it refers to % by weight of lubricating oil).

Parlkaline alkylate hydroxyl aromatic carboxylic acid salt (that is, parlkaline alkyl hydroxy benzoic acid alkali metal salt) and the second purification agent mixture system, can be present in described lubricating oil composition with minor amount compared with described lubricant viscosity base oil.Usually, its amount is about 1wt%-25wt%, and preferably about 2wt%-12wt% and more preferably from about 3wt%-8wt%, based on the gross weight of described lubricating oil composition.

Hydrocarbon based diol is preferably oil-soluble organic friction modifiers and is typically incorporated to described lubricating oil composition with the amount of the about 0.02-10.0wt.% accounting for described lubricating oil composition, preferred use 0.05-2.0wt.%, more preferably 0.05-1.0wt%, the more preferably friction improver of 0.1-0.5wt.%.

Other binder component

Following binder component is the example that advantageously can combinationally use with lubricating oil additive of the present invention.There is provided the example of these additives to set forth the present invention, but they are not intended to limit the present invention.

Dispersion agent

The dispersion agent adopted in composition of the present invention can be the mixture of ashless dispersant such as alkenyl succinimide, alkenyl succinic anhydrides, alkenyl succinate etc. or these dispersion agents.

Ashless dispersant is broadly divided into multiple kind.One class relates to multipolymer, and it contains the carboxylicesters with one or more other polar functional groups, and described polar functional group comprises amine, acid amides, imines, imide, hydroxyl, carboxyl etc.These products are prepared by the copolymerization of the monomer of chain alkyl acrylate or methacrylic ester and above-mentioned functional group.This kind comprises alkyl methacrylate-vinyl base pyrrolidinone copolymer, alkyl methacrylate-methacrylic acid dialkyl amino methacrylate copolymers etc.Additionally, high molecular acid amides and polymeric amide or ester and polyester such as tetren, polyvinyl can be adopted to gather stearate and other poly-stearylamide.Preferred dispersion agent is the long chain alkene base succinimide that N-replaces.

Single and double alkenyl succinimide derives from the reaction of alkenyl succinic or acid anhydrides and alkylene polyamine usually.The real reaction product of alkylidene group or alkylene group succsinic acid or acid anhydrides and alkylene polyamine comprises the mixture of the compound comprising succinamic acid and succinimide.But, claim this reaction product to be the succinimide of described formula traditionally, because this is the main ingredient of described mixture.The described mono-alkenyl succinimide produced and double-strand alkenyl succinimide can be depending on the polyamines of use and the charged molar ratio of amber group and concrete polyamines used.The polyamines of about 1:1 and amber group charged molar ratio can mainly manufacture order alkenyl succinimide.The polyamines of about 1:2 and amber group charged molar ratio can mainly production double-strand alkenyl succinimides.

The alkenyl succinic anhydrides obtained and alkylene polyamine, by maleic anhydride and alkenes being reacted, react to prepare by alkenyl succinimide that these N-replace subsequently.Polymkeric substance prepared by the olefinic monomer that alkenyl preferably must freely contain 2-5 carbon atom.Therefore, described alkenyl is obtained by the polymerization of the alkene containing 2-5 carbon atom to form the hydrocarbon that molecular weight is about 450-3000.These olefinic monomer examples are ethene, propylene, 1-butylene, 2-butylene, iso-butylene and their mixture.

In preferred, alkenyl succinimide is by reacting to prepare by polyalkylene succinic anhydride and alkylene polyamine.Described polyalkylene succinic anhydride is the reaction product of polyolefine (preferred polyisobutene) and maleic anhydride.Conventional polyisobutene or high methyl vinylidene polyisobutylenes can be used in this polyalkylene succinic anhydride of preparation.Heat, chlorination, free radical, acid catalysis or any other method can be used in this preparation process.The example of suitable polyalkylene succinic anhydride is U.S. Patent No. 3,361, the hot PIBSA (polyisobutenyl succinic anhydride) described in 673; U.S. Patent No. 3,172, the chlorination PIBSA described in 892; U.S. Patent No. 3,912, the heat described in 764 and the mixture of chlorination PIBSA; U.S. Patent No. 4,234, the high amber described in 435 compares PIBSA; U.S. Patent No. 5,112,507 and 5,175, the poly-PIBSA described in 225; U.S. Patent No. 5,565,528 and 5,616, the high amber described in 668 is than poly-PIBSA; U.S. Patent No. 5,286,799,5,319,030, and 5,625, the free radical PIBSA described in 004; U.S. Patent No. 4,152,499,5,137,978, and 5,137, the PIBSA prepared by high methyl vinylidene polybutene described in 980; The high amber prepared by high methyl vinylidene polybutene described in European patent application publication No. EP 355895 compares PIBSA; U.S. Patent No. 5,792, the terpolymer PIBSA described in 729; U.S. Patent No. 5,777,025 and European patent application publication No. EP 542380 in describe sulfonic acid PIBSA; With U.S. Patent No. 5,523,417 and European patent application publication No. EP 602863 in the PIBSA of purifying that describes.These documents disclosure separately is all incorporated to herein by reference at this.Described polyalkylene succinic anhydride is preferably polyisobutenyl succinic anhydride.In a preferred embodiment, described polyalkylene succinic anhydride is that number-average molecular weight is at least 450, more preferably at least 900-about 3000 and still more preferably at least about the polyisobutenyl succinic anhydride of 900-about 2300.

In another preferred embodiment of the present, the mixture of polyalkylene succinic anhydride is used.In this embodiment, described mixture preferably comprises the polyalkylene succinic anhydride component of low-molecular-weight polyalkylene succinic anhydride component and high molecular.More preferably, the number-average molecular weight of described lower-molecular-weight component is about 450 to lower than 1000 and the number-average molecular weight of described molecular weight component is 1000-about 3000.Still more preferably, low and high molecular weight component is all polyisobutenyl succinic anhydride.Alternately, various molecular weights polyalkylene succinic anhydride component may be combined with the mixture as dispersion agent and other dispersion agent as above.

Polyalkylene succinic anhydride also can be incorporated to together with purification agent, and its expection can improve stability and the consistency of purification agent mixture.When using together with purification agent, it can account for the 0.5-5 % by weight of purification agent mixture and preferred about 1.5-4 % by weight.

Described alkylene amines mainly comprises benzylidene amino, ethyleneamines, butylidene amine, propylidene amine, pentylidene amine, hexylidene amine, sub-heptyl amine, octylene amine, other polymethylene amine and also have this kind of amine ring-type with higher homologue such as piperazine and aminoalkyl group-substituted-piperazinyl.Their example is ethylene diamine, Triethylenetetramine (TETA), trimethylene diamine, decamethylene diamine, eight methylene diamine, two-heptamethylene triamine, tri propylidene tetramine, tetren, trimethylene diamine, penten, two-trimethylene triamine, 2-heptyl-3-(2-aminopropyl)-tetrahydroglyoxaline, 4-methylimidazole quinoline, N, N-dimethyl-1, 3-propylene diamine, 1, two (2-amino-ethyl) tetrahydroglyoxaline of 3-, 1-(2-aminopropyl)-piperazine, 1, two (2-amino-ethyl) piperazine of 4-and 2-methyl isophthalic acid-(2-aminobutyl) piperazine.Higher homologue such as the higher homologue by making two or more above-mentioned alkylene amines condensations obtain is useful equally.

Ethyleneamines is useful especially.They are at Encyclopedia of ChemicalTechnology, Kirk-Othmer, the 5th volume, 898-905 page (Interscience Publishers, New York, 1950) under the title " Ethylene Amines " in detailed description to a certain extent.Described term " ethyleneamines " is for representing a class polyamines with class implication, and its major part meets structural formula H ₂n (CH ₂cH ₂nH) _th, wherein t is the integer of 1-10.Therefore, it comprises such as ethylene diamine, diethylenetriamine, Triethylenetetramine (TETA), tetren, five sub-ethene hexamines etc.

Can prepare by conventional method for each alkenyl succinimide in alkenyl succinimide composition of the present invention, such as, disclosed in following United States Patent (USP): No.2,992,708; 3,018,250; 3,018,291; 3,024,237; 3,100,673; 3,172,892; 3,202,678; 3,219,666; 3,272,746; 3,361,673; 3,381,022; 3,912,764; 4,234,435; 4,612,132; 4,747,965; 5,112,507; 5,241,003; 5,266,186; 5,286,799; 5,319,030; 5,334,321; 5,356,552; 5,716,912, all disclosures are incorporated to herein by reference with all objects.

Also aftertreatment succinimide is comprised in term " alkenyl succinimide ", the people such as such as Wollenberg are in U.S. Patent No. 4,612,132 and U.S. Patent No. 4,746, disclosed in 446 grades, aftertreatment technology relates to boric acid ester or ethylene carbonate, and other aftertreatment technology, their contents whole is separately incorporated to by reference herein.Preferably, the alkenyl succinimide of described carbonic ether process is polybutylene succinimide, and it derives from, and molecular weight is 450-3000, the polybutene of preferred molecular weight be 900-2500, more preferably molecular weight to be 1300-2300, again preferred molecular weight the be mixing of 2000-2400 and these molecular weight.It is preferably by reaction conditions prepared by the unsaturation acid reagent multipolymer of polybutene succinic acid derivative, unsaturation acid reagent and alkene and the mixture reaction of polyamines, such as U.S. Patent No. 5,716, instruct in 912, be incorporated to by reference herein.

Alkenyl succinimide can be the alkenyl succinimide of modification, and it obtains by using the aftertreatments such as boric acid, alcohol, aldehyde, ketone, alkylphenol, cyclic carbonate, organic acid.The succinimide of preferred modification is boration alkenyl succinimide, and it is produced by using boric acid or boron-containing compound aftertreatment.Described boration succinimide is preferred, because their high thermal stability and oxidative stability.

Preferably, described alkenyl succinimide component accounts for 1-20 % by weight, preferably 2-12 % by weight and the more preferably 4-8 % by weight of described lubricant compositions weight.Suitable nitrogenous dispersion agent can use with the amount of 0.01-0.3 quality % by nitrogen content.

Lubricating oil and lubricating oil composition

By simply by hydrocarbon based diol of the present invention and overbased detergent mixture blended with the oil (base oil) of lubricant viscosity or mix and prepare lubricating oil composition of the present invention easily.Compound of the present invention also can as enriched material or bag with other additive various with suitable ratio pre-mixing to promote to contain lubricating composition blended expecting concentration additive.Compound of the present invention and base oil blended with certain concentration, under this concentration, they provide the fuel economy of improvement and they are both solvable in oil, also compatible with other additive in the final lubricating oil expected.Consistency typically refers to the compounds of this invention is in the case oil-soluble and other additive can not be caused under normal operation to precipitate under spendable processing rate.Oil soluble/consistency scope that the given compound of conventional dissolubility test method determination lubricant formula is suitable can be used by those skilled in the art.Such as, the precipitation of the lubricating oil composition prepared under envrionment conditions (about 20 DEG C-25 DEG C) is by being measured by the formula (which confirms being formed of insoluble Wax particles) of the actual precipitation of described oil compositions or " muddiness " solution.

The lubricating oil used in lubricating oil composition of the present invention or base oil usually according to concrete purposes as machine oil, gear oil, industry oil, cutting wet goods regulate.Such as, when crankcase engine oil expects, described base oil typically is mineral oil or synthetic oil, and its viscosity is suitable for use in the crankcase that oil engine such as petrol engine and diesel motor comprise ship engine.Crankcase oil commonly viscosity is extremely at (99 DEG C) 24cSt at 0 °F of about 1300cSt.That described lubricating oil can derive from synthesis or natural source.Natural oil plant comprises animal oil and vegetables oil (such as, Viscotrol C, lard) and mineral oil.Mineral oil as base oil of the present invention comprises paraffin, naphthenic hydrocarbon and is generally used for other oil in lubricating oil composition, comprises solvent treatment, hydrotreatment or the oil from Fischer-Tropsch method.The oil viscosity index of the preferred lubricant viscosity used in the present invention is at least 95, preferably at least 100.The grease separation of preferred lubricant viscosity from the I class of API classification oil to IV class and preferably II class, III and IV class or their optionally and the blended mixture of I class.Synthetic oil comprises hydrocarbon synthetic oil and synthetic ester.The hydrocarbon ils of useful synthesis comprises the liquid polymers of the alpha-olefin with appropriate viscosity.Useful especially is C ₆-C ₁₂the hydrogenation liquid-state oligomers such as 1-decene trimer of alpha-olefin.Similarly, the alkylbenzene of appropriate viscosity (such as two dodecylbenzene) can be used.Useful synthetic ester comprises the ester of monocarboxylic acid and polycarboxylic acid and monohydroxy alkanols and polyvalent alcohol.Typical example is hexanodioic acid two dodecyl ester, tetramethylolmethane four capronate, hexanodioic acid two-2-(ethyl hexyl) ester, sebacic acid dilauryl esters etc.Also the complex ester prepared by the mixture of monocarboxylic acid and di-carboxylic acid and monohydroxy alkanols and dihydroxyl alkanol can be used.The blend of multi mineral oil, synthetic oil and mineral oil and synthetic oil also can be favourable, such as, provide given viscosity or range of viscosities.Substantially, machine oil base oil or base oil mixture is selected to be 4-22 centistoke to make finished lube (containing various additive, comprising fuel economy compositions of additives of the present invention) the viscosity of 100 DEG C in advance.

Depend on concrete end-use and the base oil of use, typically described lubricating oil composition contains the multiple compatible additive of expectation to give finished product lubricating oil composition various character.The purification agent that such additive comprises supplementary neutrality and alkalescence such as neutral and peralkaline organic sulfonate and normally and parlkaline phenates and salicylate, dispersion agent and/or ashless dispersant.Other additive such as antiwear agents, friction improver, rust-preventive agent, froth suppressor, pour point reducer, oxidation inhibitor in addition, comprises so-called viscosity index (VI) improving agent, dispersant/VI improver and other corrodes or wear inhibitor as above.

The anti-wear agent of preferred minor amount and dialkyldisulfide join in lubricant compositions for phosphate metal salt.Described metal is preferably zinc.Described dialkyl dithiophosphate can exist with the amount of 0.1-2.0 quality %, but typically low-phosphorous composition expects, therefore the amount adopting dialkyl dithiophosphate is lower than 0.1 quality % (measuring the phosphorus level in described lubricating oil composition).Preferred use zinc dialkyl dithiophosphate (ZDDP).This provides anti-oxidant and wear-resistant character for described lubricating oil composition.This compounds can according to known technology-by first usually by alcohol or phenol and P ₂s ₅reaction forms phosphorodithioic acid, then with in suitable zn cpds and described phosphorodithioic acid-prepare.The mixture of alcohol can be used, comprise primary alconol and secondary alcohol mixture.The example of this kind of alcohol includes but not limited to following alcohol: Virahol, isooctyl alcohol, 2-butanols, methyl-isobutyl Trivalin SF (4-methyl-1-pentene-2-alcohol), 1-amylalcohol, 2-methyl butanol and 2-methyl isophthalic acid-propyl alcohol.Described alkyl can be uncle's alkyl, sechy-drocarbyl or their mixture, and such as, this compound can containing deriving from the primary alkyl of uncle or secondary carbon(atom) and/or secondary alkyl.In addition, in use, at least 50 are preferably had, more preferably 75 or more, the most preferably secondary alkyl group of 85-100 quality %; Example is the ZDDP with the secondary alkyl group of 85 quality % and 15 quality % primary alkyl-group, the ZDDP such as prepared by 85 quality % fourth-2-alcohol and 15 quality % isooctyl alcohol.It is even furthermore preferable that derive from the ZDDP and most preferably of sec-butyl alcohol and methyl-isobutyl Trivalin SF, wherein said sec-butyl alcohol is 75 % by mole.

Described dialkyldisulfide provides the phosphorus content of most (if not whole) lubricating oil composition for phosphate metal salt.Its amount in lubricating oil composition provides and represents 0.10 or less with quality % element phosphor, and preferably 0.08 or less, more preferably 0.075 or less, such as, phosphorus content in the scope of 0.025-0.07.

Oxidation retarder or oxidation inhibitor reduce the trend that oil base stock in use goes bad, and increasing by the settling of the similar varnish of oxidation products such as mud and metallic surface and viscosity proves that it goes bad.Described lubricating oil composition of the present invention contains at least one with the amount of 0.1-7 quality % further and is selected from phenolic compound (phenol oxidation inhibitor), the oxidation inhibitor of amine compound (amine oxidation inhibitor) and molybdenum compound (molybdenum oxidation inhibitor).

Hindered phenol compound is typically used as phenol oxidation inhibitor, and diaromatic amine compound is typically used as amine oxidation inhibitor.Hindered phenol antioxygen and diary Ia mine antioxidant also improve high temperature detergency all effectively.Especially, diary Ia mine antioxidant has the base number that derives from nitrogen and effectively can improve high temperature detergency.On the other hand, hindered phenol antioxygen effectively can stop oxidative degradation.

The example of hindered phenol antioxygen has 2, 6-pair-tert-butyl-para-cresol, 4, 4 '-methylene-bis (2, 6-bis--tert.-butyl phenol), 4, 4 '-methylene-bis (the 6-tertiary butyl-o-cresols), 4, 4 '-isopropylidene two (2, 6-bis--tert.-butyl phenol), 4, 4 '-bis-(2, 6-bis--tert.-butyl phenol), 2, 2 '-methylene-bis (4-methyl-6-tert-butylphenol), 4, 4 '-thiobis (2-methyl-6-tert-butylphenol), 2, two [the 3-(3 of 2-thiodiethylene, 5-bis--tert-butyl-hydroxy phenyl) propionic ester], 3-(3, 5-bis--tert-butyl-hydroxy phenyl) n-octyl propionate, 3-(3, 5-bis--tert-butyl-hydroxy phenyl) propionic acid octadecyl ester, with 3-(5-tertiary butyl-4-hydroxy-3-aminomethyl phenyl) n-octyl propionate.

The example of amine oxidation inhibitor is the alkyl diphenylamine of C4-9 mixing, p, p '-dioctyl diphenylamine, phenyl-a-naphthylamine, Phenyl beta naphthylamine, alkylation-alpha-naphthylamine, and alkylation-phenyl-a-naphthylamine.

The example of molybdenum oxidation inhibitor has the oxygen molybdenum complex of basic nitrogen compound.The example of the oxygen molybdenum complex of preferred basic nitrogen compound has the oxygen molybdenum complex of succinimide and the oxygen molybdenum complex of carboxamide.Following methods such as can be used to prepare the oxygen molybdenum complex of basic nitrogen compound, by by acid molybdenum compound or its salt and basic nitrogen compound such as succinimide, carboxamide, hydrocarbon monoamine, hydrocarbyl polyamine, Mannich hydrochloric acid, phosphonic amide, thio-phosphamide, phosphamide, dispersion type viscosity index improver (or their mixture) reacts, and temperature of reaction is remained on 120 DEG C or lower simultaneously and prepares molybdenum complex.

In addition, the molybdate compound except the oxygen molybdenum complex of basic nitrogen compound also may be used to replace the oxygen molybdenum complex of basic nitrogen compound, or combine with the oxygen molybdenum complex of basic nitrogen compound.The example of the molybdate compound of spendable mixing is sulfuration oxygen molybdenum dithiocar-bamate and sulfuration oxygen molybdenum dithiophosphates.

Phenol oxidation inhibitor (especially hindered phenol antioxygen), amine oxidation inhibitor (especially diary Ia mine antioxidant), can be used alone with molybdenum oxidation inhibitor (especially the oxygen molybdenum complex of basic nitrogen compound), or they can arbitrary combination use on demand mutually.Also these and oil-soluble antioxidants may be combinationally used.

Optionally adopt other friction improver, and it can comprise the boric acid ester, aliphatic carboxylic acid ester-acid amide, fatty phosphine acid esters, fatty alcohol (ether) phosphate, fatty Thiophosphonate, fatty thiophosphatephosphorothioate etc. of fat carboxylic ether such as glycerin fatty acid ester (example has oleic acid glyceride), glycerol fatty acid monoester of the aliphatic amide of such compound such as aliphatic amide or ethoxylation, fatty acid amide, aliphatic carboxylic acid, polyvalent alcohol, wherein aliphatic group is oil-soluble containing being greater than about 8 carbon atoms to make suitably compound usually.Below patents describe the representational example of suitable friction improver: U.S. Patent No. 3,933,659 disclose fatty acid ester and acid amides; U.S. Patent No. 4,105,571 disclose dimer fatty acid glyceride; U.S. Patent No. 4,702,859 esters disclosing carboxylic acid and acid anhydrides and alkanol; U.S. Patent No. 4,530,771, its preferred boration glyceryl monooleate comprises the ester be made up of glycerine, lipid acid and boric acid, described ester tool is the carboxylic acid remnants of 2.0 moles and the glycerine remnants of 1.5-2.0 mole at the most, by the average per unit mole boric acid remnants of the boric acid ester be used alone or in combination, described carboxylic acid remnants comprise saturated or the unsaturated alkyl group with 8-24 carbon atom, described carboxylic acid mol ratio that is remaining and described glycerine remnants counts based on 1 moles of carboxylic acids is remaining, and glycerine remnants are 1.2 moles or more; U.S. Patent No. 3,779,928 disclose alkyl group phosphonate; U.S. Patent No. 3,778,375 reaction product disclosing phosphonic acid ester and oleylamide; With U.S. Patent No. 3,932,290 reaction product disclosing two-(low alkyl group) phosphorous acid ester and epoxide.Be combined in by reference herein with the disclosure of files.The example of nitrogenous friction improver includes but not limited to tetrahydroglyoxaline, acid amides, amine, oxyalkylated amine, oxyalkylated ether amine, amine oxide acyl, amino amine, nitrile, trimethyl-glycine, quaternary amine, imines, amine salt, aminoguanidine, alkylolamide etc.This friction improver can containing being selected from straight chain, the chain of branching or the hydrocarbyl group of aromatic hydrocarbyl group or their mixture, and can be saturated or unsaturated.Hydrocarbyl group primarily of carbon and hydrogen composition, but can contain one or more heteroatoms, such as sulphur or oxygen.Preferred hydrocarbyl group is 12-25 carbon atom and can is saturated or unsaturated.More preferably there are those of linear hydrocarbyl group.

This friction improver preferably oil-soluble organic friction modifiers, described organic friction modifiers is incorporated in described lubricating oil composition with the amount accounting for described lubricating oil composition and be about 0.02-2.0wt.%.Preferred use 0.05-1.0, the more preferably described friction improver of 0.1-0.5wt.%.

Lubricating oil composition of the present invention also can contain viscosity index improver (VII).The example of viscosity index improver is poly-(alkyl methacrylate), ethylene-propylene copolymer, styrene-butadiene copolymer and polyisoprene.Also can adopt Dispersant types (there is the dispersiveness of increase) or polyfunctional viscosity index improver.These viscosity index improvers can be used alone or in combination.Viscosity index improver is incorporated to viscosity that amount in machine oil expects along with compound machine oil and changes, and usually in the scope accounting for machine oil total amount 0.5-20wt.%.

Described engine oil base oil has the outstanding Noack volatility measured according to ASTM D5800.Preferably, the Noack volatility of described engine oil base oil lower than the loss of wt%, lower than the loss of 13wt%, or lower than the loss of 11wt%.

Described engine oil base oil has the outstanding CCS viscosity at-35 DEG C measured according to ASTM D5293.Preferably, the CCS viscosity of described engine oil base oil lower than 5200mPas, lower than 5000mPas, lower than 4000mPas, lower than 3800mPas, lower than 3500mPas, lower than 3000mPas, or lower than 2500mPas.

Described engine oil base oil has at 150 DEG C according to outstanding high temperature, high-shear (HTHS) viscosity that ASTM D4683 measures.Preferably, described engine oil base oil the HTHS viscosity of 150 DEG C lower than 2.9mPas, lower than 2.6mPas, lower than 2.4mPas, lower than 2.3mPas, lower than 2.0mPas, lower than 1.9mPas, lower than 1.8mPas or lower than 1.5mPas.

Following examples are used for the specific embodiment of the present invention being described and can not being interpreted as limiting the scope of the invention by any way.

Embodiment

The present invention will be further illustrated by following examples, and described embodiment describes embodiment useful especially.Kind and the amount of the performance additive used in lubricating oil composition together with the present invention are unrestricted, and embodiment illustrated herein is only illustrative.

Embodiment 1-4 and comparative example A-D

Lubricating oil composition is prepared to be given in the formula described in table 1 and 2 by adding in binder component cited below to described base oil.The lubricating oil composition of embodiment 1-4 is according to of the present invention, and provides comparative example A-D as a comparison and be not of the present invention.Embodiment 1-3 and comparative example A-C is to reach the SAE viscosity grade (as at SAEJ300, defining in the version in 2009 January) of 0W-20 in preparation.They are 7.7-7.8mm the kinematic viscosity of 100 DEG C ²/ s.Preparation embodiment 4 and comparative example D are to reach the SAE viscosity grade of 0W-4.They are 3.1mm the kinematic viscosity of 100 DEG C ²/ s.

Ji Chu You –

A) embodiment 1-3 and comparative example A-C: (kinematic viscosity is 4.2mm at 100 DEG C to the mineral substance base oil prepared by vacuum distilling, isomerization dewaxing and hydrofining ²/ s, viscosity index is 130).

B) embodiment 4 and comparative example D: (kinematic viscosity is 3.1mm at 100 DEG C to the mineral substance base oil prepared by vacuum distilling, isomerization dewaxing and hydrofining ²/ s, viscosity index is 112)

Additive:

Fen San Ji – is ashless, nitrogenous, nitrogen content is the succinimide dispersants of 1.0wt%

Qing Jing Ji – containing metal

A) parlkaline alkyl hydroxy phenylformic acid alkaline earth salt A: calcium salt, TBN be 170 and metal ratio be 2.3, C14-18 alkyl group

B) parlkaline alkyl hydroxy phenylformic acid alkaline earth salt B: calcium salt, TBN be 230 and metal ratio be 4.0, C20-28 alkyl group

C) parlkaline alkyl hydroxy phenylformic acid alkaline earth salt C: calcium salt, TBN be 320 and metal ratio be 8.0, C20-28 alkyl group

D) overbased sulfonates A:TBN be 425 and metal ratio be 17.9 calcium sulphonate, C20-28 alkyl group

E) low peralkaline sulfonate B:TBN be 17 and metal ratio be 1.5 calcium sulphonate, C20-28 alkyl group

Friction improves Ji –

A) FM A: the vicinal diamines friction improver prepared by the mixture of 16 and 18 carbon alpha-olefins

B) FM B: the glyceryl monooleate friction improver of boration

The mixture of zinc wear inhibitor – zinc dialkyl dithiophosphate

Oxygenization presses down the mixture (Mo=5.5wt%, S=0.2wt%, N=1.6wt%) of agent – hexichol amido amine oxidation inhibitor processed and molybdenum succinimide complex compound

Nian degree index improves the polymethacrylate viscosity index improver that Ji – is used for 0W-20 formula.Viscosity index improver is not used in 0W-4 oil.

hFRR rub(bing)test

Use the frictional behaviour of lubricating oil composition described in high-frequency reciprocating instrument (HFRR) Evaluation operation example 1-3, and contrast with the frictional behaviour of the lubricating oil composition of comparative example A-C.

This HFRR experimental installation is the tribometer for measuring lubricity of industrial accreditation.PCS instrument uses electromagnetic vibrator that sample (ball) is vibrated little amplitude being simultaneously pressed on fixing sample (square position).Amplitude and frequency and the load of vibration are transformable.Measure the frictional force between described ball and square position and electrical contact resistance (ECR).Described square position, fixing sample are remained on and adds lubricating oil and in heatable bath.In the method, 2mL sample is placed in HFRR test chamber, and adjusts to standard temperature.When the temperature-stable of described sample, the vibrator arm supporting non rotatable steel ball reduces, until it contacts the test square position fully submerged in sample.This ball is forced to the square position that rubs.For this test, use the ball of the 6mm on the square position sample of 52100 steel, this tribometer is set and runs 60 minutes with 20Hz.Load is 1kg and temperature is 120 DEG C.In this test, less frictional coefficient corresponds to friction less between ball and square position.The formula of embodiment 1-3 and comparative example A-C and their respective HFRR frictional behaviour data illustrate in Table 1.

Table 1HFRR frictional behaviour

Except as otherwise noted, the value of all additives provided is in % by weight of full formula oil.Dispersion agent value represents the PPM (ppm) of the nitrogen provided by described dispersion agent.ZnDTP level is expressed as the PPM (ppm) of the phosphorus in ZnDTP.

The test-results presented in table 1 shows that the lubricating oil composition prepared according to the present invention shows the frictional behaviour of raising relative to comparative example A-C.

engine (motored) friction torque is tested

Engine friction torque test is used to evaluate frictional behaviour under the condition of boundary lubrication of embodiment 4 and comparative example D.

Petrolic bent axle (inline 4 Cylinder engines, 1.8L, roll-type valve system) is rotated by the electric motor connected by torquer, and monitoring rotary torque.The temperature of oil remains on 100 DEG C.Continue to carry out this test in 150 seconds under speed of rotation 550rpm.Moment of torsion is continued to monitor in 30 seconds after on-test to 120 second time.Mean value of torque is calculated from monitored torque value.(SAE viscosity grade 0W-20 is 8.9mm 100 DEG C of kinematic viscosity to have prepared reference oil independently ²/ s).Use 0W-20 mean value of torque as the friction torque percentage change with reference to calculating embodiment 4 and comparative example D.Embodiment 4 illustrates in table 2 with the formula of comparative example D and the friction torque percentage change of their relative 0W-20 reference oils.

Table 2 engine friction torque is tested

Except as otherwise noted, the value of all additives is the weight percent meter of the oil prepared completely.Dispersion agent value is expressed as the PPM (ppm) of the nitrogen provided by described dispersion agent.ZnDTP level is expressed as the PPM (ppm) of the phosphorus in ZnDTP.

The test-results presented in table 2 shows under final condition, to show according to the described lubricating composition of the present invention's preparation the frictional behaviour improved compared with comparative example D.The comparative example D prepared by the glyceryl monooleate friction improver of boration shows the friction of increase relative to 0W-20 reference oil.The embodiment 4 prepared by friction improver of the present invention and detergent system shows the friction of reduction.

Claims (15)

1. lubricating oil composition, comprises:

A. the base oil of the lubricant viscosity of primary amount;

B. C is selected from ₁₀-C ₃₀alkane 1,2-glycol and C ₁₀-C ₃₀the friction improver of alkene 1,2-glycol;

C. metal ratio lower than 3.0 parlkaline alkyl hydroxy phenylformic acid alkaline earth salt purification agent; With

D. metal ratio is parlkaline alkylsulphonic acid calcium or the parlkaline alkyl hydroxy calcium benzoate of 3.5 or higher.

2. lubricating oil composition according to claim 1, wherein said friction improver is selected from formula R ₁-CH (OH) CH ₂(OH), wherein R ₁for the alkyl containing 8-28 carbon atom.

3. lubricating oil composition according to claim 2, wherein said friction improver is the C of the linear alkyl derived from containing 14-18 carbon atom ₁₀-C ₃₀alkane 1,2-glycol.

4. lubricating oil composition according to claim 3, the amount of wherein said friction improver is 0.02-5.0wt.%, based on the gross weight of described lubricating oil composition.

5. lubricating oil composition according to claim 1, wherein said metal ratio is 14-18 carbon atom lower than the alkyl chain length of the parlkaline alkyl hydroxy phenylformic acid alkaline earth salt purification agent of 3.0.

6. lubricating oil composition according to claim 1, wherein said metal ratio is the parlkaline alkylsulphonic acid calcium of 3.5 or higher or the alkyl chain length of parlkaline alkyl hydroxy calcium benzoate is 20-28 carbon atom.

7. lubricating oil composition according to claim 1, wherein said metal ratio is the alkyl chain length of the parlkaline alkylsulphonic acid calcium of 3.5 or higher is 20-28 carbon atom.

8. lubricating oil composition according to claim 1, wherein said metal ratio is the alkyl chain length of the parlkaline alkyl hydroxy calcium benzoate of 3.5 or higher is 20-28 carbon atom.

9. lubricating oil composition according to claim 1, the viscosity index of the base oil of wherein said lubricant viscosity is greater than 110.

10. lubricating oil composition according to claim 9, the HTHS viscosity that the base oil of wherein said lubricating oil measures according to ASTM D4683 at 150 DEG C lower than 2.9mPas.

11. lubricating oil compositions according to claim 10, wherein prepare described lubricating oil composition to meet SAE viscosity grade 0W20.

12. lubricating oil compositions according to claim 9, wherein said lubricating oil composition according to ASTM D4683 measure HTHS viscosity at 150 DEG C lower than 2.6mPas.

13. lubricating oil compositions according to claim 9, wherein said lubricating oil composition according to ASTM D4683 measure HTHS viscosity at 150 DEG C lower than 2.3mPas.

14. lubricating oil compositions according to claim 13, wherein said lubricating oil composition contains the viscosity index improver component lower than 3wt%.

15. lubricant composition for internal combustion engine, it comprises:

A. the base oil of the lubricant viscosity of primary amount;

B. amount is the C of about 0.1-3 quality % ₁₀-C ₃₀alkyl 1,2-glycol;

C. with the alkaline earth metal content metering metal ratio that is about 0.01-0.4 quality % lower than 3.0 parlkaline alkyl (C ₁₄-C ₁₈) hydroxy-benzoic acid alkaline earth salt purification agent;

D. the metal ratio being 0.01-0.4 quality % with calcium contents metering is the parlkaline alkyl (C of 3.5 or higher ₂₀-C ₂₈) calcium sulphonate or parlkaline alkyl (C ₂₀-C ₂₈) calcium hydroxybenzoate;

E. with the nitrogenous dispersion agent of nitrogen content metering for about 0.01-0.3 quality %;

F. with the zinc dialkyl dithiophosphate that phosphorus content metering is 0.01-0.1%;

G. amount is the oxidation retarder being selected from phenolic antioxidant or diphenylamine oxidation inhibitor of 0.1-7 quality %; With

Wherein quality % is the total amount based on described lubricating oil composition.